Brown-violet azo dye.



UNITED STATES PATENT OFFICE.

PAUL JULIUS, or LUDWIGSHAFEN, GERMANY, ASSIGNOR TO BADISCHE ANILIN ANDSODA. EABRIK, OF LUDWIGSHAFEN, GERMANY.

BROWN-VIOLET AZO DYE.

SPECIFIOATION'fQrmingpart of Letters Patent N 0. 710,059, datedSeptember 30, 1902. Application filed July 1, 1902. Serial No. 114,002.(No specimens.)

To a whom it may concern;

Be it known that I, PAUL JULIUS, doctor of philosophy and chemist, asubject of the Emperor of Austria-Hungary, residing atLudwigshafen-on-the-Rhine, in the Kingdom of Bavaria, Germany, haveinvented new and bines with great difticulty,) but'does combine with iton warming the reaction liquid to, say, 50 centigrade, then yielding anew and valuable blue coloring-matter which dyes wool brown-violet"shades. The shade produced with coloring-matter equal to one per cent.of the weight of the wool dyed becomes on treatment with apotassium-bichromate solution which has been acidulatedwith acetic acida blackish blue, while the shade produced with three per cent. ofcoloring-matter .becomes on treatment with potassium bichromate andacetic acid black, with a bluish cast. On treating these aforesaidbrownviolet shades with copper sulfate, they become violet or darkviolet,-respect ively. I On reduction with stannous chlorid andhydrochloric acid my new coloring-matteryields 1.2-amido-naphthol and anamido-naphtholmono sulfo-ac'id, which acid I regard as. 2.1-

vamido-naphthol-5-sulfo-acid. The free acid .40

of the coloring-matter is difficultly soluble in cold water, morereadily soluble in boiling water, yielding a claret-red solution. Thesodium salt is soluble in water with a blue color, which on the additionof sufficient caustic soda becomes violet. The solution ofthe free acidof the coloring-matter in concentrated sulfuric acid (containing aboutninetysix per cent. of H 80 is violet.

The following example will serve to illus trate a method of carrying outmy invention; but the invention is not necessarily limited scribedtherein.

usual manner.

to this example nor to the conditions de- The parts are by weight.Example: Diazotize two hundred and fiftyseven and a half (257%) parts ofl-chlor-2-naphth-ylamin-5-sulfo-acid, or three hundred and twenty-five(325) parts of the mono-sodium salt of 2-na'phthylamin-1.5-disulfo-acidin the Add to the diazo solution or suspension so obtained suflicientsodium carbonate to neutralize the excess of mineral acid employed andalso the sulfo group or groups and then add more soda, so that an excessof one to two molecular proportions thereof is present. Allow themixture to stand forabout twelve (12) hours at a temperature of twenty(20) degrees Centigrade or for about one (1) hour at a temperature offrom fifty (50) to sixty (60) degrees centigrade. The formation of thenew diazo compound should then be finished and may be recognized by thefact that the yellowish or yellowish-red solution which results does noteasily combine with resorcin at a temperature of 0 Centigrade, butcombines with it on gently heating or on standing for some time at atemperature of about 20 centigrade, giving rise to the contained in thediam-naphthalene su1foacid,

formation of ablue-violet coloring-matter.

When this stage is reached, add a concentrated solution of from aboutone hundred and'eighty' (180) to two hundred (200) parts ofbeta-naphthol dissolved with the aid of the necessary quantity ofcaustic soda and -\var n.while stirring for about five (5) hours at atemperature of from thirty-five (35) to eighty degrees ceutigrade.'ofbeta-naphthol employed accelerates com- The excess bination, but isnot absolutely necessary. The resulting coloring-matter is for the mostpart in solution, fromwhich it can be precipi- 'tated'by the addition ofcommon salt. Filter it off and, if necessary, purifyit by dissolvingblack and on treatment with copper sulfate violet, which on reductionwith stannous chlorid and hydrochloric acid yields 1.2-amidonaphthol andan amid o naphthol-mono-sulfoacid, which coloring-matterin the form ofits free acid yields with hot water a claret solution, and withconcentrated sulfuric acid a violet solution whose sodium salt issoluble in water yielding a blue solution, which solution on theaddition of caustic soda becomes to violet.

In testimony whereof I have hereunto set my hand in'the presence of twosubscribing witnesses.

PAUL JULIUS. Witnesses:

ERNEST E. EHRHARD'I, JACOB ADRIAN.

